JP2925314B2 - Pressure sensitive adhesives based on silicone emulsion - Google Patents
Pressure sensitive adhesives based on silicone emulsionInfo
- Publication number
- JP2925314B2 JP2925314B2 JP2504436A JP50443690A JP2925314B2 JP 2925314 B2 JP2925314 B2 JP 2925314B2 JP 2504436 A JP2504436 A JP 2504436A JP 50443690 A JP50443690 A JP 50443690A JP 2925314 B2 JP2925314 B2 JP 2925314B2
- Authority
- JP
- Japan
- Prior art keywords
- weight
- acrylate
- polymer
- pressure
- sensitive adhesive
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J157/00—Adhesives based on unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C09J157/04—Copolymers in which only the monomer in minority is defined
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/068—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
- C08F290/14—Polymers provided for in subclass C08G
- C08F290/148—Polysiloxanes
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【発明の詳細な説明】 発明の背景 本発明は、初期において再位置づけが可能であり、時
間と共に永久性になりしかも耐水性を示すシリコーンア
クリレート含有アクリル系樹脂主体エマルジョン型感圧
接着剤に関するものである。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silicone acrylate-containing acrylic resin-based emulsion pressure-sensitive adhesive which can be repositioned at an early stage, becomes permanent with time, and exhibits water resistance. is there.
環境に対する関心は、魅力のある有機溶剤中での重合
とは反対の乳化又は塊状重合によって形成される感圧接
着剤重合体をもたらした。エマルジョン重合体は、基体
例えば面材料、剥離ライナー及び（又は）転写面上に被
覆させることができ、そして水の蒸発時に感圧接着剤層
が形成される。Environmental concerns have led to pressure-sensitive adhesive polymers formed by emulsion or bulk polymerization as opposed to polymerization in attractive organic solvents. The emulsion polymer can be coated on a substrate such as a face material, a release liner and / or a transfer surface, and a pressure-sensitive adhesive layer is formed upon evaporation of the water.
エマルジョン中において感圧接着剤を製造できること
は斯界において述べられている。この例としては、コフ
マン氏の米国特許第3,637,615号、スコルチ氏外の米国
特許第4,069,123号及びラゼア氏の米国特許第4,185,050
号が挙げられる。It is stated in the art that pressure sensitive adhesives can be made in emulsions. Examples include Koffman U.S. Pat.No. 3,637,615, Scorch et al. U.S. Pat.No. 4,069,123 and Lazare U.S. Pat.
No.
エマルジョン型感圧接着剤を製造できることが述べら
れているけれども、最良の発明態様を例示する際の技術
は、有機溶剤中での感圧接着性重合体の製造に固守され
ていた。この理由は、エマルジョン型接着剤の品質が貧
弱でありそしてエマルジョン型感圧接着剤が有機溶剤を
除去する方法よりも珍しい物であったという事実による
かもしれない。Although it is stated that emulsion-type pressure-sensitive adhesives can be produced, the technique in illustrating the best invention embodiment has been adhered to the production of pressure-sensitive adhesive polymers in organic solvents. This may be due to the fact that the quality of emulsion adhesives was poor and that emulsion pressure sensitive adhesives were more rare than methods that remove organic solvents.
エマルジョン型感圧接着剤は、溶剤型接着剤と比較し
て、一般に耐水性の如きある点において不十分な性能特
性を有することが判明している。本発明は、従来技術の
エマルジョン重合体の欠陥を打破するエマルジョン重合
体に向けられている。Emulsion-type pressure-sensitive adhesives have been found to have generally inadequate performance characteristics, such as water resistance, as compared to solvent-based adhesives. The present invention is directed to emulsion polymers that overcome the deficiencies of the prior art emulsion polymers.
発明の概要 発明に従えば、乳化重合体によって形成される粘着感
圧接着剤であって、アクリレート官能価数を有する共重
合含量のシリコーン重合体を含有しそして初期の再位置
づけ可能性、長期性能及び溶剤型接着剤に匹敵する性能
特性を示す粘着感圧性接着剤が提供される。SUMMARY OF THE INVENTION In accordance with the invention, there is provided a pressure-sensitive adhesive formed by an emulsion polymer, comprising a copolymeric content silicone polymer having acrylate functionality and initial repositionability, long-term performance And pressure-sensitive adhesives exhibiting performance characteristics comparable to solvent-based adhesives.
粘着性エマルジョン重合体は、粘着性重合体の総重量
を基にして、約0.1〜約１重量％好ましくは約0.2〜約0.
3重量％の反応性シリコーンアクリレート重合体３〜約
５個の炭素原子を含有する約３〜約10重量％の不飽和カ
ルボン酸、０〜約15重量％のアクリル酸メチル、０〜約
15重量％の酢酸ビニル、単量体の残部を構成する軟質単
量体好ましくはアクリル酸アルキルを含有する。好まし
いアクリル酸アルキル単量体はアクリル酸ブチル及びア
クリル酸２−エチルヘキシルであり、好ましくは、アク
リル酸ブチルは重合体アクリレートの約60〜約70重量％
の量で存在しそして重合体の約20〜30重量％はアクリル
酸２−エチルヘキシルである。The tacky emulsion polymer is about 0.1 to about 1% by weight, preferably about 0.2 to about 0.1% by weight, based on the total weight of the tacky polymer.
3% by weight of a reactive silicone acrylate polymer 3 to about 10% by weight of an unsaturated carboxylic acid containing from about 5 to 5 carbon atoms, 0 to about 15% by weight of methyl acrylate,
It contains 15% by weight of vinyl acetate, a soft monomer constituting the balance of the monomer, preferably an alkyl acrylate. Preferred alkyl acrylate monomers are butyl acrylate and 2-ethylhexyl acrylate, preferably butyl acrylate is from about 60% to about 70% by weight of the polymer acrylate.
And about 20-30% by weight of the polymer is 2-ethylhexyl acrylate.
乳化重合は、典型的には、少なくとも１種の表面活性
剤及び少なくとも１種の水溶性開始剤を含む乳化剤系の
存在下に約75〜約85℃の温度で行われる。形成される生
成物は、初期において再位置づけ可能であるがしかし時
間と共に性能を発現する。加えて、それは、優れた耐水
性又は耐湿性、耐ガソリン性及び自動車用塗料に対する
特異な接着性を示す高性能接着剤である。Emulsion polymerization is typically carried out at a temperature of about 75 to about 85 ° C in the presence of an emulsifier system comprising at least one surfactant and at least one water-soluble initiator. The product formed is initially repositionable but develops performance over time. In addition, it is a high performance adhesive that exhibits excellent water or moisture resistance, gasoline resistance and unique adhesion to automotive paints.
図面の簡単な説明 添付図面は、いかにして本発明のエマルジョン型接着
剤が初期の再位置決め可能性を示しそして接着剤が時間
と共に成長して性能を発現するかを示すものである。BRIEF DESCRIPTION OF THE DRAWINGS The accompanying drawings illustrate how the emulsion-type adhesives of the present invention show initial repositionability and that the adhesive grows over time to develop performance.
詳細な記述 本発明に従えば、エマルジョン型のアクリル樹脂系感
圧性接着剤の性能は、乳化重合を受ける単量体系の一部
分として少量の１種以上の反応性シリコーンアクリレー
ト重合体を含めることによって有意に向上される。DETAILED DESCRIPTION In accordance with the present invention, the performance of emulsion-type acrylic resin-based pressure-sensitive adhesives is significantly improved by including small amounts of one or more reactive silicone acrylate polymers as part of the monomer system that undergoes emulsion polymerization. To be improved.
用語「反応性シリコーンアクリレート重合体」は、ア
クリレート官能価数を示す重合体シロキサン及びシリコ
ーンを意味する。その例としては、アクリル化ポリシロ
キサン及びアクリル変性ポリシロキサンが挙げられる
が、しかしこれらに限定されるものではない。アクリレ
ート官能価数は、少なくとも２、好ましくは２〜約３、
典型的には約2.5〜約2.7である。多官能性シリコーンア
クリレートの例としては、米国バージニア州ホープウェ
ル所在のボールドシュミット・ケミカル・コーポレーシ
ョンによって製造販売される商品名“テゴ（Tego）シリ
コーンアクリレートRC149、300、450、710、720及び80
2"並びに“ZMR1395"を挙げることができる。これらの重
合体は、アクリレート官能価数及び約1,000〜20,000g/
モルの分子量を持つ線状ジメチルポリシロキサンであ
り、そしてその例としてはジメチルポリシロキサン及び
ペンタエリスリトールアクリレートを包含する。また、
エチル置換ポリシロキサンを用いることもできる。The term "reactive silicone acrylate polymer" refers to polymeric siloxanes and silicones that exhibit acrylate functionality. Examples include, but are not limited to, acrylated polysiloxanes and acrylic-modified polysiloxanes. The acrylate functionality is at least 2, preferably 2 to about 3,
Typically about 2.5 to about 2.7. Examples of multifunctional silicone acrylates include "Tego Silicone Acrylic RC149, 300, 450, 710, 720 and 80" manufactured and sold by Baldschmidt Chemical Corporation of Hopewell, Virginia, USA.
2 "as well as" ZMR 1395. "These polymers have an acrylate functionality of about 1,000 to 20,000 g /
It is a linear dimethylpolysiloxane having a molar molecular weight, and includes dimethylpolysiloxane and pentaerythritol acrylate. Also,
Ethyl-substituted polysiloxanes can also be used.
反応性シリコーンアクリレート重合体は、粘着性重合
体の約0.1〜約１重量％好ましくは約0.2〜約0.3重量％
の濃度で用いられる。これらは、凝集強度、低エネルギ
ー表面への接着力及び耐湿性を向上させる機能を持つ。The reactive silicone acrylate polymer comprises from about 0.1% to about 1%, preferably from about 0.2% to about 0.3%, by weight of the tacky polymer.
Used at a concentration of These have a function of improving cohesive strength, adhesion to low energy surfaces, and moisture resistance.
本発明の感圧接着剤のエマルジョン重合体中の単量体
の大半は軟質単量体であり、そしてその大半は粘着性重
合体の約50〜約95重量％の総量で存在するアクリル酸ア
ルキル単量体である。用語「軟質単量体」は、ホモ重合
したときに０℃未満のガラス転移温度を有する単量体を
意味する。挙げることができるアクリル系軟質単量体の
例は、アクリル酸ブチル、アクリル酸プロピル、アクリ
ル酸２−エチルヘキシル、アクリル酸イソオクチル、ア
クリル酸イソデシル等の如きアクリル酸アルキルを包含
する。好ましい軟質単量体は、粘着性重合体の約20〜約
30重量％の濃度で存在するアクリル酸２−エチルヘキシ
ルと組み合わさって、粘着性重合体の総量を基にして約
60〜約70％の濃度で存在するアクリル酸ブチルである。
フマル酸ジアルキルの如き他の軟質単量体も存在させて
よい。The majority of the monomers in the emulsion polymer of the pressure sensitive adhesive of the present invention are soft monomers, and the majority are alkyl acrylates present in a total amount of from about 50 to about 95% by weight of the tacky polymer. It is a monomer. The term "soft monomer" means a monomer having a glass transition temperature of less than 0 ° C when homopolymerized. Examples of acrylic soft monomers that can be mentioned include alkyl acrylates such as butyl acrylate, propyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isodecyl acrylate, and the like. Preferred soft monomers are from about 20 to about 20 of the tacky polymer.
Combined with 2-ethylhexyl acrylate present at a concentration of 30% by weight, based on the total amount of tacky polymer,
Butyl acrylate present at a concentration of 60 to about 70%.
Other soft monomers such as dialkyl fumarate may also be present.
単量体系の残部は、硬質単量体、即ち、ホモ重合させ
たときに０℃よりも高いガラス転移温度を有する単量体
から構成される。かかる単量体としては、アクリル酸メ
チル、アクリル酸エチル、メタクリル酸アルキル例えば
メタクリル酸メチル、メタクリル酸エチル、メタクリル
酸ブチル、酢酸ビニル等を挙げることができ、そしてこ
れらの各々は、粘着性重合体の０〜約15重量％好ましく
は約５〜約10重量％の量で存在しそして接着剤特性を変
性する機能を持つ。The balance of the monomer system is composed of hard monomers, ie, monomers having a glass transition temperature above 0 ° C. when homopolymerized. Such monomers include methyl acrylate, ethyl acrylate, alkyl methacrylate such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, vinyl acetate, and the like, and each of these is a tacky polymer From about 0% to about 15% by weight, preferably from about 5% to about 10% by weight, and serves to modify the adhesive properties.
また、アクリル酸、メタクリル酸、イタコン酸、フマ
ル酸の如き３〜５個好ましくは３〜約４個の炭素原子を
含有する１種以上の不飽和カルボン酸も硬質単量体とし
て存在する。これらは、凝集強度を向上させ且つ接着を
助長させる機能を持ち、そして粘着性重合体の約３〜約
10重量％好ましくは約３〜約６重量％の濃度で存在す
る。Also, one or more unsaturated carboxylic acids containing 3 to 5, preferably 3 to about 4 carbon atoms, such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, are present as hard monomers. These have the function of improving cohesive strength and promoting adhesion, and from about 3 to about
It is present at a concentration of 10% by weight, preferably about 3 to about 6% by weight.
機能性感圧接着剤であるためには、本発明に従って製
造されるエマルジョン重合体は、約−15℃よりも低い、
好ましくは約−30℃〜約−45℃、典型的には約−35℃の
正味の有効ガラス転移温度を有しなければならない。従
って、本発明の粘着性重合体の製造に用いられる各単量
体は、所定のガラス転移温度内に入る重合生成物を提供
するように釣り合わされる。この理由のために、用いる
単量体の大半として軟質単量体好ましくは１種以上のア
クリル酸アルキルが提供される。単量体の他に、多官能
性アクリレート及びメタクリレート並びに同様の架橋剤
を加えることができる。To be a functional pressure-sensitive adhesive, the emulsion polymer made in accordance with the present invention has an emulsion polymer of less than about -15C.
It should have a net effective glass transition temperature of preferably from about -30C to about -45C, typically about -35C. Thus, each monomer used in making the tacky polymer of the present invention is balanced to provide a polymerization product that falls within a predetermined glass transition temperature. For this reason, the majority of the monomers used are provided with soft monomers, preferably one or more alkyl acrylates. In addition to the monomers, polyfunctional acrylates and methacrylates and similar crosslinking agents can be added.
感圧接着剤中には、他の粘着性付与剤、充填剤、可塑
剤等を含めることができることが理解されよう。It will be appreciated that other tackifiers, fillers, plasticizers and the like can be included in the pressure sensitive adhesive.
エマルジョン型感圧接着剤中の粘着性重合体は、本発
明に従って、固形分約40〜約70重量％一般には固形分約
50〜約70重量％の範囲内の固形分含量において基体の被
覆に対して直接的な用途を有する適当なガラス転移温度
を持つ重合体を生成するように単量体を重合させること
によって製造することができる。過硫酸カリウム、第三
ブチルヒドロペルオキシド等の如き触媒は単量体100部
当り約0.15〜約0.5重量部の量で存在してよいが、」単
量体の重量を基にして約0.5〜約５重量％の範囲内の表
面活性剤レベルが好ましい。反応温度は、一般には、約
75〜約85℃の範囲内である。According to the present invention, the tacky polymer in the emulsion pressure sensitive adhesive comprises from about 40 to about 70% by weight solids,
Manufactured by polymerizing monomers to produce a polymer having a suitable glass transition temperature with a direct use for coating a substrate at a solids content in the range of 50 to about 70% by weight. be able to. Catalysts such as potassium persulfate, tertiary butyl hydroperoxide and the like may be present in an amount of about 0.15 to about 0.5 parts by weight per 100 parts of monomer, but `` about 0.5 to about 0.5 parts by weight based on the weight of monomer. Surfactant levels in the range of 5% by weight are preferred. The reaction temperature is generally about
In the range of 75 to about 85 ° C.
更に、“連鎖移動剤”を含めることができるが、この
用語は、斯界に知られるようにモノ−又はマルチメルカ
プタン基、塩素化基、ヒドロキシ基等を含有する有機化
合物を意味する。現時点で好ましい連鎖移動剤は、単量
体の約0.01〜約0.1重量％の濃度で提供されるｎ−ドデ
シルメルカプタン及びｔ−ドデシルメルカプタンであ
る。In addition, "chain transfer agents" may be included, which term refers to organic compounds containing mono- or multi-mercaptan groups, chlorinated groups, hydroxy groups, and the like, as is known in the art. Presently preferred chain transfer agents are n-dodecyl mercaptan and t-dodecyl mercaptan provided at a concentration of about 0.01 to about 0.1% by weight of the monomer.
本発明の粘着性エマルジョン重合体は、種々の基体に
対する高い保持力及び粘着力と高い凝集強度、並びに１
時間をはるかに越えた耐水斑点発生性によって示される
如き耐湿性を提供するように調製することができる。驚
いたことに、それらは、溶液重合体に匹敵する特性、即
ち、乳化重合で達成するのが困難な結果を示す。The tacky emulsion polymer of the present invention has high holding power and tackiness to various substrates, high cohesive strength,
It can be prepared to provide moisture resistance as indicated by water spotting resistance over time. Surprisingly, they show properties comparable to solution polymers, ie results which are difficult to achieve with emulsion polymerization.
単量体系の一部分として多官能性単量体及び連鎖移動
剤を含めると、内部架橋したエマルジョン重合体が生成
する。これは、カルボキシル、ヒドロキシル、アミノ及
び（又は）カルボキシル基の如き官能性基が遊離のまま
で且つ接着結合の向上に有効のままで残りそして外部架
橋反応に利用可能であり、しかも接着特性が化学線、電
子ビーム線及び（又は）外部架橋剤にさらすことによっ
て更に向上され得るという点で外部架橋重合体とは異な
る。The inclusion of a polyfunctional monomer and a chain transfer agent as part of the monomer system produces an internally crosslinked emulsion polymer. This means that functional groups such as carboxyl, hydroxyl, amino and / or carboxyl groups remain free and effective for improving the adhesive bond and are available for external cross-linking reactions, and the adhesive properties are It differs from externally crosslinked polymers in that it can be further enhanced by exposure to radiation, electron beam radiation and / or external crosslinking agents.
次の実施例は、本発明の実施態様を例示するものであ
って、本発明を限定するものではない。用いた試験方法
は、ASTM D-3654-78及びD-1000-60並びにPSTC（Pressur
e Sensitive Tape Council）テスト＃７（第８版）によ
るせん断接着力、PSTC＃１による剥離強度及びPSTC＃７
によるループ粘着性であった。The following examples illustrate embodiments of the present invention and do not limit the present invention. The test method used was ASTM D-3654-78 and D-1000-60 and PSTC (Pressur
e Sensitive Tape Council) Shear adhesive strength by test # 7 (8th edition), peel strength by PSTC # 1 and PSTC # 7
Due to loop stickiness.
例１ 重量部基準で123.71部の脱イオン水、1.30部のプロ燐
酸四ナトリウム及び27.2％の表面活性剤を含む表面活性
剤溶液を調製した。Example 1 A surfactant solution was prepared containing, based on parts by weight, 123.71 parts deionized water, 1.30 parts tetrasodium prophosphate and 27.2% surfactant.
別個に、重量％基準で157.34部のアクリル酸２−エチ
ルヘキシル、384.84部のアクリル酸ｎ−ブチル、８部の
アクリル酸メチル、16部のアクリル酸、1.63部のシリコ
ーンアクリレート（ゴールドシュミットによってCRC-30
0として販売されるもの）及び0.33部のｎ−ドデシルメ
ルカプタン（連鎖移動剤として）を含有する単量体混合
物を調製した。この単量体混合物を前記の表面活性剤溶
液に単量体４部対表面活性剤溶液１部の重量比で加え
た。Separately, on a weight% basis, 157.34 parts 2-ethylhexyl acrylate, 384.84 parts n-butyl acrylate, 8 parts methyl acrylate, 16 parts acrylic acid, 1.63 parts silicone acrylate (CRC-30 by Goldschmidt)
A monomer mixture containing 0.33 parts of n-dodecyl mercaptan (as sold as chain transfer agent) and 0.33 parts of n-dodecyl mercaptan was prepared. This monomer mixture was added to the surfactant solution at a weight ratio of 4 parts monomer to 1 part surfactant solution.
別個に、85重量部の脱イオン水と２重量部の過硫酸カ
リウムと少量の表面活性剤との添加用触媒溶液を調製し
た。Separately, a catalyst solution for addition of 85 parts by weight of deionized water, 2 parts by weight of potassium persulfate and a small amount of a surfactant was prepared.
窒素ブランケット下の撹拌機付きの反応器に、190重
量部の脱イオン水、4.10重量部の表面活性剤及び1.43部
の過硫酸カリウムの仕込みに続いて、単量体及び表面活
性剤溶液に触媒溶液を、僅かな発熱量で反応を実施でき
るようにする割合で少しずつ加えた。温度を80±２℃に
保つと、約57.7％の全固形分含量を有するエマルジョン
が形成された。次いで、エマルジョンを殺生剤（バイオ
サイド）−アンモニア中和用溶液で6.8〜7.1のpHに調節
した。表１は、このエマルジョン接着剤の特性を市販の
溶液型接着剤と比較するものである。溶液型接着剤の対
照は、モンサント社によって“モンサント−1753"とし
て製造販売されているものである。A reactor with a stirrer under a nitrogen blanket was charged with 190 parts by weight of deionized water, 4.10 parts by weight of surfactant and 1.43 parts of potassium persulfate, and then catalyzed to monomer and surfactant solution. The solution was added in small portions at a rate that allowed the reaction to run with a slight exotherm. Maintaining the temperature at 80 ± 2 ° C. formed an emulsion with a total solids content of about 57.7%. The emulsion was then adjusted to pH 6.8-7.1 with a biocide-ammonia neutralizing solution. Table 1 compares the properties of this emulsion adhesive with commercially available solution adhesives. The solution adhesive control is manufactured and sold by Monsanto as "Monsanto-1753".
添付図面は、時間に応じた180°剥離接着力の変化を2
6g/m2の被覆重量の函数として例示するものであるが、
重合体と粘着性付与剤との総重量を基にして23重量％の
レベルで“フォラル（Foral）85"を添加して粘着性を付
与した場合及び43g/m2の被覆重量の場合も示す。面材料
は２ミルのマイヤーであり、そして乾燥は85℃で10分間
であった。 The attached drawing shows the change in 180 ° peel adhesion according to time.
But it is intended to illustrate a coating weight function of 6 g / m 2,
Shows the case of a total weight at the level of based on 23% by weight by adding "Foraru (Foral) 85" coating weight when imparted with tackiness and 43 g / m 2 of the polymer and the tackifier . The face material was 2 mil Meyer and drying was at 85 ° C for 10 minutes.
表２は、500gの荷重をかけた0.5in×0.5in試料を使用
して３つの組成標準について行なった70℃での２°せん
断接着力を示すものである。Table 2 shows the 2 ° shear adhesion at 70 ° C. performed on three composition standards using a 0.5 inch × 0.5 inch sample under a 500 g load.
表２ 被覆重量 70℃における２° せん断接着力，分 26g/m2 600〜750 43g/m2 600〜700 26g/m2,23％フォラル85 10〜15 例２ 例１の操作を本質的に反復したが、但し、乾燥基準で
用いた単量体組成は次の如くであった。 Table 2 2 ° shear adhesion at 70 ° C coating weight , min 26 g / m 2 600-750 43 g / m 2 600-700 26 g / m 2 , 23% foral 85 10-15 Example 2 Essentially the operation of Example 1 The procedure was repeated, except that the monomer composition used on a dry basis was as follows.
単量体 重量部 アクリル酸２−エチルヘキシル 113.99 アクリル酸ブチル 362.06 酢酸ビニル 78.55 アクリル酸メチル 6.17 アクリル酸 13.56 ｎ−ドデシルメルカプタン 0.55 シリコーンアクリレート （１） 1.50 トリプロピレングリセロールジアクリレート 9.13 １）ゴールドシュミットRC802 ３〜４のpHにおいて78〜82℃で３時間にわたって反応
を行ない、その後に６〜７のpHに中和した。固形分含量
は58〜69％であった。 Monomer parts by weight 2-ethylhexyl acrylate 113.99 Butyl acrylate 362.06 Vinyl acetate 78.55 Methyl acrylate 6.17 Acrylic acid 13.56 n-Dodecyl mercaptan 0.55 Silicone acrylate (1) 1.50 Tripropylene glycerol diacrylate 9.13 1) Goldschmidt RC802 3-4 The reaction was carried out at 78-82 ° C for 3 hours at a pH of 5 and then neutralized to a pH of 6-7. The solids content was 58-69%.
例３ 単量体系を次の如き重量部で用いて例１の操作を再び
反復した。Example 3 The procedure of Example 1 was repeated again, using the monomer system in parts by weight as follows.
単量体 重量部 アクリル酸２−エチルヘキシル 115. アクリル酸ブチル 374. メタクリル酸 7.30 アクリル酸 17.90 ｎ−ドデシルメルカプタン 0.35 シリコーンアクリレート （１） 6.5 78〜81℃の温度で反応を行なうと、２ミルの“マイラ
ー”上に25〜30g/m2の被覆重量に流延したときに、１時
間を越えた耐水斑点性を有し、そして２時間後にのみ僅
かな斑点が発生する生成物が得られた。 Parts by weight of monomer 2-ethylhexyl acrylate 115. butyl acrylate 374. methacrylic acid 7.30 acrylate 17.90 n-dodecylmercaptan 0.35 silicone acrylate (1) 6.5 when cast coating weight of 25-30 g / m 2 on mylar ", has a water spot resistance in excess of 1 hour, and the product was obtained a slight spots occurs only after 2 hours.
例４ 例３の単量体系を使用して例１の操作を本質上反復し
たが、但し、シリコーンアクリレート単量体は単量体の
2.9重量％の量で存在するゴールドシュミットRC-450で
あった。耐水斑点性は１〜３時間であり、そして500g荷
重における70℃での２°せん断接着力は1,440分を越え
ていた。Example 4 The procedure of Example 1 was essentially repeated using the monomer system of Example 3, except that the silicone acrylate monomer was
Goldschmidt RC-450 present in an amount of 2.9% by weight. The water spot resistance was 1-3 hours, and the 2 ° shear adhesion at 70 ° C. at 500 g load exceeded 1,440 minutes.
例５ シリコーンアクリレート単量体含量が全単量体の2.9
部であったことを除いて例４の操作を反復すると、提供
される感圧接着剤重合体は70℃において１〜３時間の耐
水斑点性を示し、500g荷重での２°せん断接着力は1,00
0〜1,400分以上そして100℃では18〜500分であった。Example 5 Silicone acrylate monomer content was 2.9 of all monomers
Repeating the procedure of Example 4 except that the parts were water-resistant, the pressure-sensitive adhesive polymer provided exhibited water spot resistance at 70 ° C. for 1-3 hours and a 2 ° shear bond at 500 g load of 1,00
0-1400 minutes or more and at 100 ° C. 18-500 minutes.
例６ 例４の操作を反復したが、但し、シリコーンアクリレ
ート単量体として、単量体の約2.4重量部の濃度で存在
する“ゴールドシュミットRC-300"を用いた。耐水斑点
性は再び１〜３時間であり、そして２°せん断接着力は
70℃において1,440分を越えていた。Example 6 The procedure of Example 4 was repeated except that "Goldschmidt RC-300", which is present at a concentration of about 2.4 parts by weight of the monomer, was used as the silicone acrylate monomer. The water spot resistance is again 1-3 hours, and the 2 ° shear adhesion is
It exceeded 1,440 minutes at 70 ° C.
例７ シリコーンアクリレートとして、単量体の約２重量部
の濃度で存在するゴールドシュミットRC-300及び単量体
の0.3重量部の濃度で存在するドデシルメルカプタンを
使用すると、例６と本質上同じ結果が得られた。耐水斑
点性は再び１〜３時間であり、そして70°での２°せん
断接着力は1,440分を越えていた。Example 7 Using as a silicone acrylate Goldschmidt RC-300 present at a concentration of about 2 parts by weight of monomer and dodecyl mercaptan present at a concentration of 0.3 part by weight of monomer, essentially the same results as in Example 6 was gotten. Water spot resistance was again 1-3 hours, and 2 ° shear adhesion at 70 ° exceeded 1,440 minutes.
例８ 例７と本質上同じ操作を反復したが、但しシリコーン
アクリレート含量（RC-300）は単量体の約1.7重量部で
あった。再び耐水斑点性は１〜３時間であり、これに対
して２°せん断接着力は初期には1,440分以上そして70
℃で３ケ月後には8000分を越えていた。100℃における
初期の２°せん断接着力は500分を越えていた。Example 8 Essentially the same procedure was repeated as in Example 7, except that the silicone acrylate content (RC-300) was about 1.7 parts by weight of monomer. Again the water spot resistance is 1-3 hours, whereas the 2 ° shear adhesion is initially more than 1,440 minutes and 70
After 3 months at ℃, it exceeded 8000 minutes. The initial 2 ° shear adhesion at 100 ° C. was over 500 minutes.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 昭48−102188（ＪＰ，Ａ) 特開 平１−98602（ＪＰ，Ａ) 特開 平２−308807（ＪＰ，Ａ) 特開 平３−76713（ＪＰ，Ａ) 特開 平３−81311（ＪＰ，Ａ) 特開 昭49−32933（ＪＰ，Ａ) 米国特許4333867（ＵＳ，Ａ) 米国特許4716194（ＵＳ，Ａ) 米国特許4693935（ＵＳ，Ａ) (58)調査した分野(Int.Cl.6，ＤＢ名) C09J 1/00 - 201/10 C08F 290/00 - 290/14 C08F 20/00 - 20/70 C08F 220/00 - 220/70 ──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-48-102188 (JP, A) JP-A-1-98602 (JP, A) JP-A-2-308807 (JP, A) JP-A-3-3 76713 (JP, A) JP-A-3-81313 (JP, A) JP-A-49-32933 (JP, A) US Patent 4,338,673 (US, A) US Patent 4,716,194 (US, A) US Patent 4,693,935 (US, A) (58) Field surveyed (Int. Cl. 6 , DB name) C09J 1/00-201/10 C08F 290/00-290/14 C08F 20/00-20/70 C08F 220/00-220/70
Claims (18)
数を有する少なくとも１種の反応性シリコーンアクリレ
ート重合体と、 （ｂ）３〜５個の炭素原子を含有する少なくとも１種の
不飽和カルボン酸と、 （ｃ）少なくとも１種のアクリル酸アルキル軟質単量体
と、 の乳化重合によって製造された粘着性重合体からなる感
圧接着剤であって、 シリコーンアクリレート重合体の総量が粘着性重合体の
0.1〜１重量％であり、不飽和カルボン酸の総量が粘着
性重合体の３〜10重量％であり、そしてアクリル酸アル
キル軟質単量体の総量が粘着性重合体の少なくとも50重
量％であり、しかも該粘着性重合体が−15℃よりも低い
ガラス転移温度を有することからなる感圧接着剤。1. A polymer comprising: (a) at least one reactive silicone acrylate polymer having at least 2 acrylate functionality; and (b) at least one unsaturated carboxylic acid containing from 3 to 5 carbon atoms. (C) a pressure-sensitive adhesive comprising a tacky polymer produced by emulsion polymerization of at least one kind of an alkyl acrylate soft monomer, wherein the total amount of the silicone acrylate polymer is a tacky polymer of
0.1 to 1% by weight, the total amount of unsaturated carboxylic acids is 3 to 10% by weight of the tacky polymer, and the total amount of alkyl acrylate soft monomers is at least 50% by weight of the tacky polymer. And a pressure-sensitive adhesive, wherein the adhesive polymer has a glass transition temperature lower than -15 ° C.
〜３のアクリレート官能価数を有する請求の範囲第１項
記載の感圧接着剤。2. The method of claim 1, wherein the reactive silicone acrylate polymer is 2
The pressure-sensitive adhesive of claim 1 having an acrylate functionality of from 3 to 3.
1,000〜20,000g/モルの分子量を有する線状ジメチルポ
リシロキサンである請求の範囲第１項記載の感圧接着
剤。3. The reactive silicone acrylate polymer according to claim 1,
2. The pressure-sensitive adhesive according to claim 1, which is a linear dimethylpolysiloxane having a molecular weight of 1,000 to 20,000 g / mol.
重合体の0.2〜0.3重量％の濃度で存在する請求の範囲第
２項記載の感圧接着剤。4. A pressure-sensitive adhesive according to claim 2, wherein the reactive silicone acrylate is present in a concentration of from 0.2 to 0.3% by weight of the tacky polymer.
重合体の0.2〜0.3重量％の濃度で存在する請求の範囲第
３項記載の感圧接着剤。5. A pressure-sensitive adhesive according to claim 3, wherein the reactive silicone acrylate is present in a concentration of from 0.2 to 0.3% by weight of the tacky polymer.
〜６重量％である請求の範囲第１項記載の感圧接着剤。6. An adhesive polymer having an unsaturated carboxylic acid content of 3
2. The pressure-sensitive adhesive according to claim 1, wherein the amount is from about 6% by weight to about 6% by weight.
ビニル及びこれらの混合物よりなる群から選択される少
なくとも１種の硬質単量体が０〜15重量％存在する請求
の範囲第１項記載の感圧接着剤。7. The adhesive polymer according to claim 1, wherein at least one hard monomer selected from the group consisting of methyl acrylate, vinyl acetate and a mixture thereof is present in an amount of 0 to 15% by weight. The pressure-sensitive adhesive as described.
ル、アクリル酸２−エチルヘキシル及びこれらの混合物
よりなる群から選択される請求の範囲第１項記載の感圧
接着剤。8. The pressure-sensitive adhesive according to claim 1, wherein the alkyl acrylate is selected from the group consisting of butyl acrylate, 2-ethylhexyl acrylate, and mixtures thereof.
ブチル及び20〜30重量％のアクリル酸２−エチルヘキシ
ルからなる請求の範囲第１項記載の感圧接着剤。9. The pressure-sensitive adhesive according to claim 1, wherein the tacky polymer comprises 60 to 70% by weight of butyl acrylate and 20 to 30% by weight of 2-ethylhexyl acrylate.
価数を有する少なくとも１種の反応性シリコーンアクリ
レート重合体と、 （ｂ）３〜４個の炭素原子を含有する少なくとも１種の
不飽和カルボン酸と、 （ｃ）アクリル酸メチルと、 （ｄ）酢酸ビニルと、 （ｅ）アクリル酸ブチルと、 （ｆ）アクリル酸２−エチルヘキシルと、 の乳化重合によって製造された粘着性重合体からなる感
圧接着剤であって、 シリコーンアクリレート重合体の総量が粘着性重合体の
0.1〜１重量％であり、不飽和カルボン酸の総量が粘着
性重合体の３〜10重量％であり、アクリル酸メチルの量
が粘着性重合体の０〜15重量％であり、酢酸ビニルの量
が粘着性重量体の０〜15重量％であり、アクリル酸ブチ
ルの量が粘着性重合体の60〜70重量％であり、そしてア
クリル酸２−エチルヘキシルの量が粘着性重合体の20〜
30重量％であり、 しかも該粘着性重合体が−15℃よりも低いガラス転移温
度を有することからなる感圧接着剤。10. (a) at least one reactive silicone acrylate polymer having at least 2 acrylate functionality; and (b) at least one unsaturated carboxylic acid containing 3 to 4 carbon atoms. And (c) methyl acrylate; (d) vinyl acetate; (e) butyl acrylate; and (f) 2-ethylhexyl acrylate. An adhesive, wherein the total amount of the silicone acrylate polymer is
0.1 to 1% by weight, the total amount of unsaturated carboxylic acid is 3 to 10% by weight of the tacky polymer, the amount of methyl acrylate is 0 to 15% by weight of the tacky polymer, The amount is from 0 to 15% by weight of the tacky weight, the amount of butyl acrylate is from 60 to 70% by weight of the tacky polymer, and the amount of 2-ethylhexyl acrylate is from 20 to
30% by weight, and wherein said tacky polymer has a glass transition temperature lower than -15 ° C.
２〜３のアクリレート官能価数を有する請求の範囲第10
項記載の感圧接着剤。11. The method of claim 10 wherein the reactive silicone acrylate polymer has an acrylate functionality of 2-3.
Item.
が、1,000〜20,000g/モルの分子量を有する線状ジメチ
ルポリシロキサンである請求の範囲第10項記載の感圧接
着剤。12. The pressure-sensitive adhesive according to claim 10, wherein the reactive silicone acrylate polymer is a linear dimethylpolysiloxane having a molecular weight of 1,000 to 20,000 g / mol.
性重合体の0.2〜0.3重量％の濃度で存在する請求の範囲
第11項記載の感圧接着剤。13. The pressure-sensitive adhesive according to claim 11, wherein the reactive silicone acrylate is present in a concentration of from 0.2 to 0.3% by weight of the tacky polymer.
性重合体の0.2〜0.3重量％の濃度で存在する請求の範囲
第12項記載の感圧接着剤。14. The pressure-sensitive adhesive according to claim 12, wherein the reactive silicone acrylate is present in a concentration of from 0.2 to 0.3% by weight of the tacky polymer.
量が３〜６重量％である請求の範囲第10項記載の感圧接
着剤。15. The pressure-sensitive adhesive according to claim 10, wherein the polymerizable unsaturated carboxylic acid content of the adhesive polymer is 3 to 6% by weight.
求の範囲第10項記載の感圧接着剤。16. The pressure-sensitive adhesive according to claim 10, wherein the unsaturated carboxylic acid is acrylic acid.
求の範囲第14項記載の感圧接着剤。17. The pressure-sensitive adhesive according to claim 14, wherein the unsaturated carboxylic acid is acrylic acid.
求の範囲第15項記載の感圧接着剤。18. The pressure-sensitive adhesive according to claim 15, wherein the unsaturated carboxylic acid is acrylic acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US315,507 | 1989-02-24 | ||
| US07/315,507 US4994538A (en) | 1989-02-24 | 1989-02-24 | Siliconized emulsion based pressure-sensitive adhesives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03505233A JPH03505233A (en) | 1991-11-14 |
| JP2925314B2 true JP2925314B2 (en) | 1999-07-28 |
Family
ID=23224746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2504436A Expired - Fee Related JP2925314B2 (en) | 1989-02-24 | 1990-02-20 | Pressure sensitive adhesives based on silicone emulsion |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US4994538A (en) |
| EP (1) | EP0412152B1 (en) |
| JP (1) | JP2925314B2 (en) |
| KR (1) | KR0181474B1 (en) |
| AT (1) | ATE129725T1 (en) |
| AU (1) | AU630432B2 (en) |
| CA (1) | CA2010112C (en) |
| DE (1) | DE69023292T2 (en) |
| WO (1) | WO1990010028A1 (en) |
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| US5264278A (en) * | 1991-03-20 | 1993-11-23 | Minnesota Mining And Manufacturing Company | Radiation-curable acrylate/silicone pressure-sensitive adhesive coated tapes adherable to paint coated substrates |
| JPH06506014A (en) * | 1991-03-20 | 1994-07-07 | ミネソタ マイニング アンド マニュファクチャリング カンパニー | Radiation curable vinyl/silicone release coating |
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| EP2909270A1 (en) | 2012-10-22 | 2015-08-26 | Avery Dennison Corporation | Hybrid material of crosslinked microgel particles dispersed in an adhesive |
| JP5940221B2 (en) * | 2012-11-06 | 2016-06-29 | エルジー・ケム・リミテッド | Acrylic-silicone hybrid emulsion pressure-sensitive adhesive composition and method for producing the same |
| CN104371607B (en) * | 2013-08-12 | 2016-08-17 | 湖北航天化学技术研究所 | High-solid-content and low-viscosity acrylate emulsion stick and preparation method |
| CA2981362A1 (en) | 2015-04-15 | 2016-10-20 | Avery Dennison Corporation | Non-pvc label film for printing |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4112213A (en) * | 1964-09-28 | 1978-09-05 | Johnson & Johnson | Pressure sensitive adhesive tapes and method of making same |
| US3575910A (en) * | 1965-08-25 | 1971-04-20 | Dow Corning | Siloxane-acrylate copolymers and emulsions thereof |
| US3707518A (en) * | 1968-07-11 | 1972-12-26 | Johnson & Johnson | Acrylate adhesive tape and composition |
| US3617362A (en) * | 1968-07-11 | 1971-11-02 | Johnson & Johnson | Acrylate adhesive tape and composition |
| US3551391A (en) * | 1968-12-09 | 1970-12-29 | Johnson & Johnson | Modified acrylate adhesive product |
| US3558574A (en) * | 1968-12-09 | 1971-01-26 | Johnson & Johnson | Acrylated adhesive products |
| US3729438A (en) * | 1970-03-30 | 1973-04-24 | Union Carbide Corp | Latex polymers of vinylacetate and a silane |
| US3808287A (en) * | 1970-09-08 | 1974-04-30 | Dow Corning | Siloxane-acrylate copolymers |
| US4147685A (en) * | 1977-01-28 | 1979-04-03 | General Electric Company | Primer compositions for adhering silicone compositions |
| GB2070629B (en) * | 1980-03-03 | 1983-08-24 | Scott Bader Co | Ceramic tile adhesives |
| DE3227552A1 (en) * | 1982-07-23 | 1984-01-26 | Dynamit Nobel Ag, 5210 Troisdorf | COPOLYMERISATE WITH ETHYLENICALLY UNSATURATED BASIC BLOCKS AND SEVERAL FUNCTIONAL GROUPS |
| US4693933A (en) * | 1983-06-06 | 1987-09-15 | Ovonic Synthetic Materials Company, Inc. | X-ray dispersive and reflective structures and method of making the structures |
| JPS60228517A (en) * | 1984-04-26 | 1985-11-13 | Kanegafuchi Chem Ind Co Ltd | Novel polymer and its production |
| US4716194A (en) * | 1985-11-25 | 1987-12-29 | National Starch And Chemical Corporation | Removable pressure sensitive adhesive |
| FR2603590B1 (en) * | 1986-02-25 | 1991-05-24 | Kansai Paint Co Ltd | PROCESS FOR THE PREPARATION OF A RESIN CONTAINING A POLYSILOXANE |
| US4693935A (en) * | 1986-05-19 | 1987-09-15 | Minnesota Mining And Manufacturing Company | Polysiloxane-grafted copolymer pressure sensitive adhesive composition and sheet materials coated therewith |
| JPS6411167A (en) * | 1987-07-02 | 1989-01-13 | Toray Silicone Co | Covering material composition |
-
1989
- 1989-02-24 US US07/315,507 patent/US4994538A/en not_active Expired - Lifetime
-
1990
- 1990-02-15 CA CA002010112A patent/CA2010112C/en not_active Expired - Fee Related
- 1990-02-20 WO PCT/US1990/001035 patent/WO1990010028A1/en active IP Right Grant
- 1990-02-20 AT AT90904151T patent/ATE129725T1/en not_active IP Right Cessation
- 1990-02-20 AU AU51940/90A patent/AU630432B2/en not_active Ceased
- 1990-02-20 EP EP90904151A patent/EP0412152B1/en not_active Expired - Lifetime
- 1990-02-20 JP JP2504436A patent/JP2925314B2/en not_active Expired - Fee Related
- 1990-02-20 KR KR1019900702323A patent/KR0181474B1/en not_active IP Right Cessation
- 1990-02-20 DE DE69023292T patent/DE69023292T2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| EP0412152A1 (en) | 1991-02-13 |
| KR0181474B1 (en) | 1999-05-01 |
| AU5194090A (en) | 1990-09-26 |
| US4994538A (en) | 1991-02-19 |
| DE69023292T2 (en) | 1996-06-27 |
| AU630432B2 (en) | 1992-10-29 |
| JPH03505233A (en) | 1991-11-14 |
| CA2010112A1 (en) | 1990-08-24 |
| EP0412152A4 (en) | 1991-08-14 |
| ATE129725T1 (en) | 1995-11-15 |
| KR920700248A (en) | 1992-02-19 |
| CA2010112C (en) | 2002-02-05 |
| EP0412152B1 (en) | 1995-11-02 |
| WO1990010028A1 (en) | 1990-09-07 |
| DE69023292D1 (en) | 1995-12-07 |
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| LAPS | Cancellation because of no payment of annual fees |